Stereospecific Protodeauration/Transmetalation Generating Configurationally Stable P‐Metalated Nucleoside Derivatives

Highly efficient transmetalation between gold phosphites and iodopalladium species is presented. In addition to successful transfer of cyclic and acyclic phosphites, studies involving P‐chiral substrates revealed that an initial protodeauration as well as the target transmetalation were both stereospecific, and that the overall process occurred with retention of configuration at phosphorus. Building on the mechanistic work, a catalytic approach to the synthesis of chiral P‐arylated nucleoside derivatives was developed. This chemistry has the potential to be easily adapted for the preparation of a diverse group of P‐chiral species. A stereospecific protodeauration/transmetalation sequence facilitated the synthesis of configurationally stable P‐metalated species. Mechanistic studies using model systems revealed the overall process to occur with retention of stereochemistry. This methodology was adapted for the synthesis of chiral P‐arylated nucleoside derivatives.